JPWO2019177120A1 - Base material with membrane - Google Patents

Abstract

Providing a base material with a film having excellent fingerprint stain removing property and slip resistance. The base material with a film of the present invention includes a base material and a film having a poly (oxyfluoroalkylene) chain arranged only in a part of a region on the main surface of the base material.

Description

The present invention relates to a substrate with a film.

Fluorine-containing compounds are preferably used as surface treatment agents because they exhibit high lubricity, water and oil repellency, and the like. When water and oil repellency is imparted to the surface of the base material by the surface treatment agent, it becomes easy to wipe off the dirt on the surface of the base material, and the dirt removal property is improved. Among the above-mentioned fluorine-containing compounds, the fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain in which an ether bond (-O-) is present in the middle of the fluoroalkylene chain is a compound having excellent flexibility, and particularly, such as fats and oils. Excellent in removing dirt.
As the fluorine-containing ether compound, a compound having a poly (oxyperfluoroalkylene) chain and a hydrolyzable silyl group at the terminal is widely used (Patent Document 1).

International Publication No. 2014/069592

The surface treatment agent containing the fluorine-containing ether compound is used in applications where it is required to maintain the performance (fingerprint stain removing property) that can be easily removed by wiping off the fingerprints adhering to the surface for a long time. Such applications include, for example, a surface treatment agent for a member that constitutes a surface (for example, a display screen or a surface opposite to the display screen (back surface)) that is touched by a finger or palm of a smartphone or the like.
The present inventors evaluated a substrate with a film in which a film obtained by using a fluorine-containing ether compound was arranged on the entire main surface of the substrate. As a result, the fingerprint stain removing property was good, but the slip resistance was inferior. I found that (that is, slippery). For example, if the base material with a film is a smartphone, the smartphone may slip and be damaged when the smartphone is operated or placed on a desk or the like.

In view of the above problems, it is an object of the present invention to provide a base material with a film having excellent fingerprint stain removing property and slip resistance.

As a result of diligent studies on the above problems, the present inventor has found that a desired effect can be obtained by arranging a film having a poly (oxyfluoroalkylene) chain only on a part of the main surface of the base material. It came to.
That is, the present inventor has found that the above problem can be solved by the following configuration.

[1] A film-attached substrate having a substrate and a film having a poly (oxyfluoroalkylene) chain arranged only in a part of the main surface of the substrate.
[2] The membrane-coated substrate according to [1], wherein the membrane is a membrane obtained by using a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a reactive silyl group.
[3] A first region in which a film having a poly (oxyfluoroalkylene) chain is arranged and a second region in which a film having a poly (oxyfluoroalkylene) chain is not arranged. The film-coated substrate according to [1] or [2], wherein the area ratio (area of the first region / area of the second region) is 0.3 to 50.0.
[4] The substrate with a film according to any one of [1] to [3], wherein the substrate is a touch panel substrate or a display substrate.
[5] The film according to any one of [1] to [4], wherein the base material is made of glass and the coverage of the film having a poly (oxyfluoroalkylene) chain on the main surface is 20 to 97%. With base material.
[6] The film-coated substrate according to any one of [1] to [5], wherein the film is arranged in a plurality of dotted regions on the main surface of the substrate.
[7] The film-coated substrate according to [6], wherein the plurality of dot-shaped regions are arranged in a checkered flag shape.
[8] The film-coated substrate according to any one of [1] to [5], wherein the film is arranged in a band-shaped region on the main surface of the substrate.
[9] The base material has a peripheral region and a central region surrounded by the peripheral region on the main surface thereof, and the film is arranged in the central region [1] to [5]. The substrate with a film according to any one of.
[10] The base material has a plurality of point-like dispersion regions and continuous regions other than the dispersion regions on the main surface thereof, and the film is arranged in the continuous regions [1]. ] To the substrate with a film according to any one of [5].

According to the present invention, it is possible to provide a substrate with a film having excellent fingerprint stain removing property and slip resistance.

It is a top view which shows an example of the substrate with a film of this invention. It is a schematic perspective view which shows an example of the substrate with a film of this invention. It is a top view which shows an example of the substrate with a film of this invention. It is a top view which shows an example of the substrate with a film of this invention. It is a top view which shows an example of the substrate with a film of this invention. It is a top view which shows an example of the substrate with a film of this invention.

In the present specification, the unit represented by the formula (1) is referred to as a unit (1). Units expressed by other formulas are also described in the same manner. The group represented by the formula (2) is referred to as the group (2). The groups represented by other formulas are also described in the same manner. The compound represented by the formula (3) is referred to as compound (3). Compounds represented by other formulas are also described in the same manner.
In the present specification, when "the alkylene group may have an A group", the alkylene group may have an A group between carbon atoms in the alkylene group, or the alkylene group-. It may have an A group at the end, such as A group.

The meanings of the terms in the present invention are as follows.
The "divalent organopolysiloxane residue" is a group represented by the following formula. ^{R x} in the following formula is an alkyl group (preferably 1 to 10 carbon atoms) or a phenyl group. Further, g1 is an integer of 1 or more, preferably an integer of 1 to 9, and particularly preferably an integer of 1 to 4.

The “silphenylene skeleton group” is a group represented by −Si (R ^y ) ₂ PhSi (R ^y ) _2- (where Ph is a phenylene group and R ^y is a monovalent organic group). Is. As R ^y , an alkyl group (preferably 1 to 10 carbon atoms) is preferable.
A "dialkylsilylene group" is a group represented by −Si (R ^z ) _2- (where R ^z is an alkyl group (preferably having 1 to 10 carbon atoms)).
The "number average molecular weight" of a compound is calculated by determining the number (mean value) of oxyfluoroalkylene groups with respect to the terminal groups by ¹ H-NMR and ^{19 F-NMR.}

The base material with a film of the present invention (hereinafter, also referred to as "base material with a main film") is a base material and a poly (oxyfluoroalkylene) chain arranged only in a part of a region on the main surface of the base material. (Hereinafter, also referred to as "first film").
In the following description, the first membrane is the main surface of the substrate that may be used in contact with other articles or human fingers and / or may be held by human fingers during operation. The arranged surface is called the "main surface". The main surface is not limited to a flat surface.
Of the main surface of the base material, the region where the first film is arranged is also referred to as "first region", and the region where the first film is not arranged is also referred to as "second region".
A film-coated substrate having a film having a poly (oxyfluoroalkylene) chain on the main surface has excellent fingerprint stain removing property as compared with a surface made of another material (for example, glass), but has dynamic friction. The coefficient tends to be low. Therefore, by arranging the film having the poly (oxyfluoroalkylene) chain as described above only in a part of the main surface of the base material, excellent fingerprint stain removing property can be maintained and excellent slip resistance can be maintained. It is presumed that we were able to secure.

〔Base material〕
The substrate may be another article (eg, stylus), a substrate that may be used in contact with a person's fingers, a substrate that may be held by a person's fingers during operation, and / or other articles (eg, a stylus). , A base material that may be placed on a mounting table) is preferable. A base material that is required to have water and oil repellency is particularly preferable because it can impart water and oil repellency. Specific examples of the material of the base material include metals, resins, glasses, sapphires, ceramics, stones, hydrophilic films, and composite materials thereof. The glass may be chemically strengthened.
As the base material, a touch panel base material and a display base material are preferable, and a touch panel base material is particularly preferable. The base material for the touch panel preferably has translucency. “Having translucency” means that the vertically incident visible light transmittance according to JIS R3106: 1998 (ISO 9050: 1990) is 25% or more. Glass and transparent resin are preferable as the material of the base material for the touch panel.
Further, examples of the base material include the following. Used for building materials, decorative building materials, interior goods, transportation equipment (for example, automobiles), signs / bulletin boards, drinkers / tableware, water tanks, ornamental equipment (forehead, boxes), laboratory equipment, furniture, art / sports / games. Glass and resin, glass and resin used for exterior parts (excluding display parts) in devices such as mobile phones (for example, smartphones), personal digital assistants, game machines, and remote controls are also preferable. The shape of the base material may be plate-like or film-like.

[First film]
The first film is a film having a poly (oxyfluoroalkylene) chain and is arranged only in a part of the main surface of the base material.
The first film may be formed directly on the main surface of the base material, or may be formed on the base material via another film formed on the main surface of the base material. As a specific example of the above other film, a base film formed on the main surface of the base material by subjecting the base material with the compound described in paragraphs 0008 to 0905 of International Publication No. 2011/016458, SiO _{2 or the like.} Can be mentioned.

The poly (oxyfluoroalkylene) chain contains a plurality of units represented by the following formula (1).
(OX) ・ ・ ・ (1)

X is a fluoroalkylene group having one or more fluorine atoms.
The number of carbon atoms of the fluoroalkylene group is preferably 1 to 6 and particularly preferably 2 to 4 from the viewpoint of more excellent weather resistance and corrosion resistance of the film.
The fluoroalkylene group may be linear or branched, but is preferably linear because the effect of the present invention is more excellent.
The fluoroalkylene group preferably has 1 or more fluorine atoms and is more excellent in corrosion resistance of the film, and preferably 2 to 10 groups, particularly preferably 2 to 4 groups.
The fluoroalkylene group may be a group in which all hydrogen atoms in the fluoroalkylene group are substituted with fluorine atoms (perfluoroalkylene group).

Specific examples of the unit _{(1), -OCHF -, -} OCF 2 CHF -, - OCHFCF 2 -, - OCF 2 CH 2 -, - OCH 2 CF 2 -, - OCF 2 CF 2 CHF -, - OCHFCF 2 CF _2- , -OCF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CH _2- , -OCH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- , _{-OCF 2 -, - OCF 2 CF} 2 -, - OCF 2 CF 2 CF 2 -, - OCF (CF 3) CF 2 -, - OCF 2 CF 2 CF 2 CF 2 -, - OCF (CF 3) CF 2 CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CF _2- , -OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- .

The number m1 of the unit (1) contained in the poly (oxyfluoroalkylene) chain is 2 or more, an integer of 2 to 200 is more preferable, an integer of 5 to 150 is further preferable, and an integer of 5 to 100 is particularly preferable. , 10 to 50 are most preferred.
The poly (oxyfluoroalkylene) chain may contain only one unit (1) or may contain two or more units (1). Examples of two or more types of units (1) include two or more types of units (1) having different carbon numbers, and two or more types of units having the same carbon number but different side chains and different types of side chains. (1) Two or more units (1) having the same number of carbon atoms but different numbers of fluorine atoms can be mentioned.
The binding order of two or more types of (OX) is not limited, and may be arranged randomly, alternately, or in blocks.

The poly (oxyfluoroalkylene) chain is preferably a poly (oxyfluoroalkylene) chain mainly composed of the unit (1) which is an oxyperfluoroalkylene group in order to obtain a film having excellent fingerprint stain removing property. (OX) In the _{poly (oxyfluoroalkylene) chain represented by m1} , the ratio of the number of units (1) which are oxyperfluoroalkylene groups to the total number m1 of units (1) may be 50 to 100%. It is preferably 80 to 100%, more preferably 90 to 100%.

(OX) As _m1 , [(OCH _ma F _(2-ma) ) _m11 · (OC ₂ H _mb F _(4-mb) ) _m12 · (OC ₃ H _mc F _(6-mc) ) _m13 · (OC) ₄ H _md F _(8-md) ) _m14 · (OC ₅ H _me F _(10-me) ) _m15 · (OC ₆ H _mf F _(12-mf) ) _m16 ] is preferable.
ma is 0 or 1, mb is an integer from 0 to 3, mc is an integer from 0 to 5, md is an integer from 0 to 7, me is an integer from 0 to 9, and mf is an integer from 0 to 9. It is an integer from 0 to 11.
m11, m12, m13, m14, m15 and m16 are each independently an integer of 0 or more, preferably 100 or less.
m11 + m12 + m13 + m14 + m15 + m16 are integers of 2 or more, preferably an integer of 2 to 200, more preferably an integer of 5 to 150, further preferably an integer of 5 to 100, and particularly preferably an integer of 10 to 50.
Among them, m12 is preferably an integer of 2 or more, and an integer of 2 to 200 is particularly preferable.
In addition, C ₃ H _mb F _(6-mb) , C ₄ H _mc F _(8-mc) , C ₅ H _md F _(10-md) and C ₆ H _me F _(12-me) are all available. It may be linear or branched chain, and linear is preferable from the viewpoint of more excellent abrasion resistance of the film.

The above equation represents the type of unit and its number, and does not represent an array of units. That is, m11 to m15 represent the number of units, for example, (OCH _ma F _(2-ma) ) _m11 represents a block in which (OCH _ma F _(2-ma) ) units are m11 consecutive. is not it. Similarly, _{the description order of (OCH ma} F _(2-ma) ) to (OC ₆ H _mf F _(12-mf) ) does not indicate that they are arranged in the description order.
In the above formula, when 2 or more of m11 to m15 are not 0 (that is, when (OX) _m1 is composed of two or more units), the sequences of different units are random sequences, alternating sequences, block sequences and It may be any combination of these sequences.
Further, each of the above units may also be different if the unit includes two or more units. For example, when m11 is 2 or more, a plurality of (OCH _ma F _(2-ma) ) may be the same or different.

The first membrane is preferably a membrane obtained by using a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a reactive silyl group. The reactive silyl group means a hydrolyzable silyl group and a silanol group (Si-OH). The reactive silyl group is preferably the group (2) represented by the following formula (2). The fluorine-containing ether compound may be used alone or in combination of two or more.
The definition of the poly (oxyfluoroalkylene) chain is as described above.
−Si (R) _n L _3-n ... (2)

The number of groups (2) contained in the fluorine-containing ether compound is 1 or more, and 2 or more is preferable, 2 to 10 is more preferable, and 2 to 5 is more preferable in that the friction resistance of the film is more excellent. More preferably, 2 or 3 are particularly preferable.
When there are a plurality of groups (2) in one molecule, the plurality of groups (2) may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of fluorine-containing ether compounds, they are preferably the same.

R is a monovalent hydrocarbon group, preferably a monovalent saturated hydrocarbon group. The carbon number of R is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 to 2.

L is a hydrolyzable group or a hydroxyl group.
A hydrolyzable group is a group that becomes a hydroxyl group by a hydrolyzing reaction. That is, the hydrolyzable silyl group becomes a silanol group represented by Si-OH by the hydrolysis reaction. The silanol groups further react between the silanol groups to form a Si—O—Si bond. Further, the silanol group can form a chemical bond (base material-O-Si) by dehydration condensation reaction with a hydroxyl group (base material-OH) on the surface of the base material.

Specific examples of L, which is a hydrolyzable group, include an alkoxy group, a halogen atom, an acyl group, and an isocyanate group (-NCO). As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom, a chlorine atom is preferable.
As L, an alkoxy group having 1 to 4 carbon atoms and a halogen atom are preferable from the viewpoint that the fluorine-containing ether compound can be more easily produced. As L, an alkoxy group having 1 to 4 carbon atoms is preferable because there is little outgassing during coating and the storage stability of the fluorine-containing ether compound is more excellent, and when long-term storage stability of the fluorine-containing ether compound is required. The ethoxy group is particularly preferable, and the methoxy group is particularly preferable when the reaction time after coating is short.

n is an integer of 0 to 2.
n is preferably 0 or 1, and 0 is particularly preferable. The presence of a plurality of L makes the adhesion of the film to the substrate stronger.
When n is 1 or less, the plurality of Ls present in one molecule may be the same or different. From the viewpoint of easy availability of raw materials and ease of production of fluorine-containing ether compounds, they are preferably the same. When n is 2, the plurality of Rs present in one molecule may be the same or different. From the viewpoint of the availability of raw materials and the ease of producing a fluorine-containing ether compound, it is preferable that a plurality of R's are the same.

As the fluorine-containing ether compound, the compound (3) represented by the following formula (3) is preferable because it is excellent in water and oil repellency and abrasion resistance of the film.
[A- (OX) _m1- ] _j Z [-Si (R) _n L _3-n ] _g ... (3)

A is a perfluoroalkyl group or -Q [-Si (R) _n L _3-n ] _k .
The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and particularly preferably 1 to 3 from the viewpoint of more excellent abrasion resistance of the film.
The perfluoroalkyl group may be linear or branched.
However, when A is −Q [−Si (R) _n L _3-n ] _k , j is 1.

Perfluoroalkyl groups include CF _3- , CF ₃ CF _2- , CF ₃ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF (CF ₃ )-and the like can be mentioned.
_{As the perfluoroalkyl group, CF 3} −, CF ₃ CF ₂ −, and CF ₃ CF ₂ CF ₂ − are preferable because the film has more excellent water and oil repellency.

Q is a linking group of (k + 1) valence. As will be described later, k is an integer of 1 to 10. Therefore, as Q, a linking group having a valence of 2 to 11 can be mentioned.
The Q may be a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, or a silicon atom that may have an ethereal oxygen atom or a divalent organopolysiloxane residue. , 2-8 valent organopolysiloxane residues, and Si (R) from formulas (3-1A), formulas (3-1B), formulas (3-1A-1) to (3-1A-6) described below. ) _{Groups excluding n} L _3-n can be mentioned.

The definitions of R, L, n, X and m1 are as described above.

Z is a (j + g) valence linking group.
Z may be a group that does not impair the effects of the present invention, for example, an alkylene group, a carbon atom, a nitrogen atom, a silicon atom, which may have an ethereal oxygen atom or a divalent organopolysiloxane residue. 2 to 8 valent organopolysiloxane residues, and formulas (3-1A), formulas (3-1B), formulas (3-1A-1) to (3-1A-6) to Si (R) described later. _{Groups excluding n} L _3-n can be mentioned.

j is an integer of 1 or more, and an integer of 1 to 5 is preferable from the viewpoint of more excellent water and oil repellency of the film, and 1 is particularly preferable from the viewpoint of easy production of the compound (3).
g is an integer of 1 or more, and an integer of 2 to 4 is preferable, 2 or 3 is more preferable, and 3 is particularly preferable, from the viewpoint that the abrasion resistance of the film is more excellent.

The compound (3) is preferably a compound represented by the following formula (3-1) from the viewpoint of having more excellent water and oil repellency of the film.
A- (OX) _m1- Z ³¹ ... (3-1)
In formula (3-1), the definitions of A, X and m1 are synonymous with the definitions of each group in formula (3).

Z ³¹ is a group (3-1A) represented by the following formula (3-1A) or a group (3-1B) represented by the following formula (3-1B).
-Q ^a- X ³¹ (-Q ^b- Si (R) _n L _3-n ) _h (-R ³¹ ) _i ... (3-1A)
−Q ^c − [CH ₂ C (R ³² ) ( ^{−Q d} −Si (R) _n L _3-n )] _y −R ³³ ... (3-1B)

Q ^a is a single bond or divalent linking group.
Examples of the divalent linking group include a divalent hydrocarbon group, a divalent heterocyclic group, -O-, -S-, -SO _2- , -N (R ^d )-, and -C (O). −, −Si ( ^Ra ) ₂ −, and groups in which two or more of these are combined can be mentioned. Here, ^Ra is an alkyl group (preferably 1 to 10 carbon atoms) or a phenyl group. R ^d is a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
Examples of the divalent hydrocarbon group include a divalent saturated hydrocarbon group, a divalent aromatic hydrocarbon group, an alkenylene group, and an alkynylene group. The divalent saturated hydrocarbon group may be linear, branched or cyclic, and examples thereof include an alkylene group. The number of carbon atoms of the divalent saturated hydrocarbon group is preferably 1 to 20. The divalent aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. As the alkenylene group, an alkenylene group having 2 to 20 carbon atoms is preferable, and as the alkynylene group, an alkynylene group having 2 to 20 carbon atoms is preferable.
Examples of the group in which two or more of these are combined include -OC (O)-, -C (O) N (R ^d )-, an alkylene group-O-alkylene group, and an alkylene group -OC (O). -Alkylene group, alkylene group-Si ( ^Ra ) ₂ -phenylene group-Si ( ^Ra ) ₂ can be mentioned.

X ³¹ is a single bond, alkylene group, carbon atom, nitrogen atom, silicon atom or 2-8 valent organopolysiloxane residue.
The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.
The carbon number of the alkylene group represented by X ³¹ is preferably 1 to 20, and particularly preferably 1 to 10.
Examples of the 2 to 8 valent organopolysiloxane residue include a divalent organopolysiloxane residue and a (w + 1) -valent organopolysiloxane residue described later.

Q ^b is a single bond or divalent linking group.
Definition of the divalent linking group are the same as those defined as described in the above-described Q ^a.

R ³¹ is a hydroxyl group or an alkyl group.
The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.

When X ³¹ is a single bond or an alkylene group, h is 1 and i is 0.
When X ³¹ is a nitrogen atom, h is an integer of 1 to 2, i is an integer of 0 to 1, and h + i = 2 is satisfied.
When X ³¹ is a carbon atom or a silicon atom, h is an integer of 1 to 3, i is an integer of 0 to 2, and h + i = 3 is satisfied.
When X ³¹ is a 2 to 8 valent organopolysiloxane residue, h is an integer of 1 to 7, i is an integer of 0 to 6, and h + i = 1 to 7 is satisfied.
When h is 2 or more, the two or more (-Q ^b- Si (R) _n L _3-n ) may be the same or different. When i is 2 or more, the two or more (-R ³¹ ) may be the same or different.

Q ^c is a single bond, an alkylene group, or an alkylene group having an ethereal oxygen atom between carbon atoms and having 2 or more carbon atoms, and a single bond is preferable from the viewpoint of easy production of a compound.
The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
The carbon number of an alkylene group having 2 or more carbon atoms having an ethereal oxygen atom between carbon atoms is preferably 2 to 10 and particularly preferably 2 to 6.

R ³² is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is preferable from the viewpoint of easy production of a compound.
As the alkyl group, a methyl group is preferable.

Q ^d is a single bond or an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. From the viewpoint of easy production of a compound, Q ^d is preferably a single bond or −CH _2−.

R ³³ is a hydrogen atom or a halogen atom, and a hydrogen atom is preferable because it is easy to produce a compound.

y is an integer of 1 to 10, and an integer of 1 to 6 is preferable.
Two or more [CH ₂ C (R ³² ) (−Q ^d − Si (R) _n L _3-n )] may be the same or different.

As the group (3-1A), the groups (3-1A-1) to (3-1A-6) are preferable.
-(X ³² ) _s1- Q ^b1 _{-SiR n} L _3-n ... (3-1A-1)
-(X ³³ ) _s2- Q ^a2- N [-Q ^b2 -Si (R) _n3 L _3-n ] ₂ ... (3-1A-2)
−Q ^a3 −G (R ^g ) [ ^{−Q b3} −Si (R) _n L _3-n ] ₂ ... (3-1A-3)
− [C (O) N (R ^d )] _s4 −Q ^a4- (O) _t4 −C [− (O) _u4 −Q ^b4 −Si (R) _n L _3-n ] ₃ ... (3-) 1A-4)
−Q ^a5 −Si [−Q ^b5 −Si (R) _n L _3-n ] ₃ ... (3-1A-5)
− [C (O) N (R ^d )] _v −Q ^a6 −Z ^a [−Q ^b6 −Si (R) _n L _3-n ] _w ... (3-1A-6)
The definitions of R, L, and n in the formulas (3-1A-1) to (3-1A-6) are as described above.

In formula (3-1A-1), X ³² is -O- or -C (O) N (R ^d )-(where N in the formula is bound to ^{Q b1).}
The definition of R ^d is as described above.
s1 is 0 or 1.

Q ^b1 is an alkylene group. The alkylene group may have —O—, a silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group. The alkylene group may have a plurality of groups selected from the group consisting of -O-, a silphenylene skeleton group, a divalent organopolysiloxane residue and a dialkylsilylene group.
When the alkylene group has an —O—, silphenylene skeleton group, a divalent organopolysiloxane residue or a dialkylsilylene group, it is preferable to have these groups between carbon atoms.

The carbon number of the alkylene group represented by Q ^b1 is preferably 1 to 10, and particularly preferably 2 to 6.

As for Q ^b1 , when s1 is 0, −CH ₂ OCH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ − is preferable. (X ³² ) When _s1 is −O−, −CH ₂ CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable. (X ³² ) When _s1 is −C (O) N (R ^d ) −, an alkylene group having 2 to 6 carbon atoms is preferable (however, N in the formula is bonded to ^{Q b1).} If Q ^b1 is these groups, the compound can be easily produced.

Specific examples of the group (3-1A-1) include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

In formula (3-1A-2), X ³³ is -O-, -NH-, or -C (O) N (R ^d )-.
The definition of R ^d is as described above.

Q ^a2 is a single bond, an alkylene group, -C (O)-, or an ethereal oxygen atom between carbon atoms and carbon atoms, -C (O)-, -C (O) O-, -OC (O). )-Or -NH- is an alkylene group having 2 or more carbon atoms.
The carbon number of the alkylene group represented by Q ^a2 is preferably 1 to 10, and particularly preferably 1 to 6.
2 or more carbon atoms having an ethereal oxygen atom, -C (O)-, -C (O) O-, -OC (O)-or -NH-, represented by ^{Qa2, between carbon atoms.} The number of carbon atoms of the alkylene group is preferably 2 to 10, and particularly preferably 2 to 6.

The Q ^a2, from the viewpoint of easily producing the _{compound, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 -, - CH 2 NHCH 2 CH 2 -, -CH ₂ CH ₂ OC (O) CH ₂ CH _2- , -C (O)-is preferable (however, the right side is bound to N).

s2 is 0 or 1 (where Q ^a2 is 0 when it is a single bond). 0 is preferable from the viewpoint that the compound can be easily produced.

Q ^b2 is an alkylene group or an alkylene group having 2 or more carbon atoms having a divalent organopolysiloxane residue, an etheric oxygen atom or -NH- between carbon atoms and carbon atoms.
The carbon number of the alkylene group represented by Q ^b2 is preferably 1 to 10, and particularly preferably 2 to 6.
The number of carbon atoms of an alkylene group having 2 or more carbon atoms having a divalent organopolysiloxane residue, an etheric oxygen atom or -NH- between carbon atoms and carbon atoms represented by ^{Q b2 is 2 to 10.} 2 to 6 are preferable, and 2 to 6 are particularly preferable.

As Q ^b2 _{, −CH 2} CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound (however, the right side binds to Si).

The two [−Q ^b2 −Si (R) _n L _3-n ] may be the same or different.

Specific examples of the group (3-1A-2) include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

In the formula (3-1A-3), Q ^a3 is a single bond, an alkylene group, or an alkylene group having an ether oxygen atom between carbon atoms and having 2 or more carbon atoms, which facilitates the production of a compound. From the point of view, a single bond is preferable.
The carbon number of the alkylene group represented by Q ^a3 is preferably 1 to 10, and particularly preferably 2 to 6.
Represented by Q ^a3, carbon atoms - the number of carbon atoms of the alkylene group having 2 or more carbon atoms and having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.

G is a carbon atom or a silicon atom.
R ^g is a hydroxyl group or an alkyl group. The number of carbon atoms of the alkyl group represented by ^{R g is preferably 1 to 4.}
As G (R ^g ), C (OH) or Si (R ^ga ) (however, R ^ga is an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, preferably methyl, from the viewpoint of easy production of a compound. The group is particularly preferable.) Is preferable.

Q ^b3 is an alkylene group or an alkylene group having 2 or more carbon atoms having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms.
The carbon number of the alkylene group represented by Q ^b3 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of an alkylene group having 2 or more carbon atoms and having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms represented by ^{Q b3 is preferably 2 to 10 and 2 to 6} Is particularly preferable.
As Q ^b3 _{, −CH 2} CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound.

The two [−Q ^b3 −Si (R) _n L _3-n ] may be the same or different.

Specific examples of the group (3-1A-3) include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

In formula (3-1A-4), ^{the definition of R d} is as described above.
s4 is 0 or 1.
Q ^a4 is a single bond, an alkylene group, or an alkylene group having 2 or more carbon atoms having an ethereal oxygen atom between carbon atoms.
Q ^a4 number of carbon atoms of the alkylene group represented by 1 to 10 is preferred, 1 to 6 is particularly preferred.
Represented by Q ^a4, carbon atoms - the number of carbon atoms of the alkylene group having 2 or more carbon atoms and having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
t4 is 0 or 1 (where Q ^a4 is 0 when it is a single bond).
As for −Q ^a4- (O) _t4- , when s4 is 0, a single bond, −CH ₂ O− _{, −CH 2} OCH ₂ −, −CH ₂ OCH ₂ CH ₂ O-, -CH ₂ OCH ₂ CH ₂ OCH _2- , -CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH _2- is preferable (however, the left side is ^{bonded to (R f} O) _m ), and s4 is 1. In the case of, single bond, −CH ₂ − _{, −CH 2} CH ₂ − is preferable.

Q ^b4 is an alkylene group, and the alkylene group is -O-, -C (O) N (R ^d )-( ^{the definition of R d} is as described above), a silphenylene skeleton group, and a divalent group. It may have an organopolysiloxane residue or a dialkylsilylene group.
When the alkylene group has an —O— or sylphenylene skeletal group, it is preferable to have an —O— or sylphenylene skeletal group between carbon atoms. When the alkylene group has a -C (O) N (R ^d )-, dialkylsilylene group or a divalent organopolysiloxane residue, it is between carbon atoms or the end on the side that binds to _{(O) u4.} It is preferable to have these groups in.
The carbon number of the alkylene group represented by Q ^b4 is preferably 1 to 10, and particularly preferably 2 to 6.

u4 is 0 or 1.
- _(O) u4 ^{-Q b4} - as it is from the viewpoint of easily producing the _{compound, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 CH 2 -, - CH 2 OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ −, −OCH ₂ CH ₂ CH ₂ −, −OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ −, −OSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ PhSi (CH ₃ ) ₂ CH ₂ CH ₂ − are preferable (however, the right side is bonded to Si).

The three [-(O) _u4- Q ^b4- Si (R) _n L _3-n ] may be the same or different.

Specific examples of the group (3-1A-4) include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

In the formula (3-1A-5), Q ^a5 is an alkylene group or a carbon atom - is the number 2 or more alkylene groups having an etheric oxygen atom between carbon atoms.
The carbon number of the alkylene group represented by Q ^a5 is preferably 1 to 10, and particularly preferably 2 to 6.
Represented by Q ^a5, carbon atoms - the number of carbon atoms of the alkylene group having 2 or more carbon atoms and having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
The Q ^a5, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH ₂ -is preferable (however, the right side is bonded to Si).

Q ^b5 is an alkylene group or an alkylene group having 2 or more carbon atoms having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms.
The carbon number of the alkylene group represented by Q ^b5 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of an alkylene group having 2 or more carbon atoms and having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms represented by ^{Q b5 is preferably 2 to 10 and 2 to 6} Is particularly preferable.
As Q ^b5 _{, −CH 2} CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound (however, the right side is Si (R) _n L _3-n). Combine with.).

The three [-Q ^b5- Si (R) _n L _3-n ] may be the same or different.

Specific examples of the group (3-1A-5) include the following groups. In the following formula, * represents the bonding position with _{(OX) m1.}

In formula (3-1A-6), ^{the definition of R d} is as described above.
v is 0 or 1.

Q ^a6 is an alkylene group or an alkylene group having 2 or more carbon atoms having an ethereal oxygen atom between carbon atoms.
The carbon number of the alkylene group represented by Q ^a6 is preferably 1 to 10, and particularly preferably 2 to 6.
Represented by Q ^a6, carbon atoms - the number of carbon atoms of the alkylene group having 2 or more carbon atoms and having an etheric oxygen atom between carbon atoms, preferably 2 to 10, 2 to 6 is particularly preferred.
The Q ^a6, from the viewpoint of easily producing the _{compound, -CH 2 OCH 2 CH 2 CH} 2 -, - CH 2 OCH 2 CH 2 OCH 2 CH 2 CH 2 -, - CH 2 CH 2 -, - CH 2 CH ₂ CH ₂ - is preferred (but the right side is attached to ^{Z a.).}

Z ^a is an organopolysiloxane residue of (w + 1) valence.
w is an integer of 2 to 7.
Examples of the (w + 1) -valent organopolysiloxane residue include the following groups. ^{However, Ra} in the following equation is as described above.

Q ^b6 is an alkylene group or an alkylene group having 2 or more carbon atoms having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms.
The carbon number of the alkylene group represented by Q ^b6 is preferably 1 to 10, and particularly preferably 2 to 6.
The carbon number of an alkylene group having 2 or more carbon atoms and having an ethereal oxygen atom or a divalent organopolysiloxane residue between carbon atoms represented by ^{Q b6 is preferably 2 to 10 and 2 to 6} Is particularly preferable.
As Q ^b6 _{, −CH 2} CH ₂ − and −CH ₂ CH ₂ CH ₂ − are preferable from the viewpoint of easy production of a compound.

The w [−Q ^b6 −Si (R) _n3 L _3-n ] may be the same or different.

Compound 3 is preferably a compound represented by the formula (3-2) from the viewpoint of having more excellent water and oil repellency of the film.
[A- (OX) _m1- Q ^a- ] _j32 Z ³² [-Q ^b- Si (R) _n L _3-n ] _h32 ... (3-2)
The definitions of A, X, m1, Q ^a , Q ^b , R, and L in formula (3-2) are synonymous with the definitions of each group in formula (3-1) and formula (3-1A). Is.

Z ³² is a (j32 + h32) -valent hydrocarbon group or a (j32 + h32) -valent hydrocarbon group having two or more carbon atoms having one or more ethereal oxygen atoms between carbon atoms.
As Z ³² , a residue obtained by removing the hydroxyl group from the polyhydric alcohol having a primary hydroxyl group is preferable.
As Z ³² , groups represented by formulas (Z-1) to (Z-5) are preferable from the viewpoint of easy availability of raw materials. However, R ³⁴ is an alkyl group, preferably a methyl group or an ethyl group.

j32 is an integer of 2 or more, and an integer of 2 to 5 is preferable because the water and oil repellency of the film is more excellent. H32 is an integer of 1 or more, and the abrasion resistance of the film is more excellent. An integer of 4 is preferred, 2 or 3 is more preferred.

Specific examples of the fluorine-containing ether compound include those described in the following documents.
Perfluoropolyether-modified aminosilane described in JP-A-11-209585,
Silicon-containing organic fluoropolymers described in Japanese Patent No. 2874715,
Organosilicon compounds described in JP-A-2000-144097,
Perfluoropolyether-modified aminosilane described in JP-A-2000-327772,
Fluorinated siloxane described in JP-A-2002-506887,
The organic silicone compound described in JP-A-2008-534696,
Fluorinated modified hydrogen-containing polymer according to Japanese Patent No. 4138936,
Compounds described in U.S. Patent Application Publication No. 2010/0129672, International Publication No. 2014/126064, JP-A-2014-0701163,
The organosilicon compounds described in International Publication No. 2011/060047 and International Publication No. 2011/059430,
Fluorine-containing organosilane compound according to International Publication No. 2012/064694,
Fluoroxyalkylene group-containing polymer described in JP2012-722272.
International Publication No. 2013/042732, International Publication No. 2013/121984, International Publication No. 2013/121985, International Publication No. 2013/121986, International Publication No. 2014/163004, Japanese Patent Application Laid-Open No. 2014-080473, International Publication No. Fluorine-containing ether compounds according to No. 2015/087902, International Publication No. 2017/038830, International Publication No. 2017/038832, International Publication No. 2017/187775,
Perfluoro (poly) ether-containing silane compounds according to JP-A-2014-218369, International Publication No. 2017/022437, International Publication No. 2018/079743, International Publication No. 2018/143433,
Fluoropolyether group-containing polymer-modified silanes described in JP-A-2015-199906, JP-A-2016-204656, JP-A-2016-210854, and JP-A-2016-222859.
In International Publication No. 2018/216630, International Publication No. 2019/039226, International Publication No. 2019/039341, International Publication No. 2019/039186, Japanese Patent Application No. 2017-167973, Japanese Patent Application No. 2017-167999, Japanese Patent Application No. 2017-251611 Fluorine-containing ether compound according to the above.

Commercially available products of fluorine-containing ether compounds include KY-100 series (KY-178, KY-185, KY-195, etc.) manufactured by Shin-Etsu Chemical Co., Ltd., Afluid (registered trademark) S550 manufactured by AGC, and Daikin Industries, Ltd. Optool (registered trademark) DSX, Optool (registered trademark) AES, Optool (registered trademark) UF503, Optool (registered trademark) UD509 and the like.

(form)
The form (shape) of the first film is not particularly limited, but any one of the following or a combination thereof is preferable from the viewpoint of being more excellent in the effect of the present invention. Hereinafter, a suitable form of the first film will be described with reference to the drawings. 1 to 6 are examples in which a plate-shaped base material is used.

FIG. 1 is a schematic plan view showing an example of a substrate with a film of the present invention. As shown in FIG. 1, the film-attached base material 10 has a base material 12 and a first film 14 arranged in a plurality of dotted first regions 12a on the main surface of the base material 12. The second region 12b on the main surface of the base material 12 is exposed on the main surface of the base material 10 with a film.
Here, the main surface of the plate-shaped base material 12 means the surface of one of the plurality of surfaces constituting the base material 12. Specifically, as shown in FIG. 2 (schematic perspective view of the base material 10 with a film), when the base material 12 has a plate shape, two surfaces perpendicular to the thickness direction t of the base material 12 (Surface 12X, surface 12Y; in other words, two main surfaces), which means one surface (in the example of FIG. 2, surface 12X, in other words, one main surface). The case of the main surface of the base material in FIGS. 3 to 6 below is synonymous with the meaning of the main surface of the base material in FIG.

The shape of the first film 14 is circular, but is not limited to, for example, an elliptical shape, an oval shape, an intersecting oval shape, a polygon (for example, a triangle, a quadrangle, a pentagon, a hexagon, etc.). It may be a cross shape, a star shape), or a rounded corner shape having rounded corners of the above polygon. Among these, from the viewpoint of manufacturing efficiency of the first film 14, it is preferably circular, oval or quadrangular.
The shapes of the plurality of first films 14 may be the same or different from each other, but are preferably the same as shown in FIG.
The size of the first film 14 is preferably 10 to 1500 μm, more preferably 50 to 800 μm, from the viewpoint that the effect of the present invention is more excellent. Here, the size of the first film 14 means the diameter of the first film 14 when it is circular, and means the equivalent circle diameter calculated from the area of the first film 14 when it is not circular. To do.
The sizes of the plurality of first films 14 may be the same or different from each other, but are preferably the same as shown in FIG.
The first film 14 is arranged in a square grid at equal intervals, but is not limited to this, and is arranged in a grid other than the square grid (for example, a hexagonal grid, a rectangular grid, or an orthorhombic grid). It may be arranged or randomly arranged. The distance between the adjacent first films 14 is preferably 10 to 1500 μm, particularly preferably 50 to 1000 μm, from the viewpoint that the effect of the present invention is more excellent.

FIG. 3 is a schematic plan view showing an example of the base material with a film of the present invention. Specifically, FIG. 3 is an embodiment in which the first film is arranged in a plurality of punctate first regions on the main surface of the base material. It is a figure which shows the modification. The configuration of the film-attached base material 20 of FIG. 3 is different from the shape of the first region of the film-attached base material 10 of FIG. 1 except that the shape of the first region of the film-attached base material 20 of FIG. The structure is almost the same as that of the base material 10.
As shown in FIG. 3, the first film 24 is arranged in the first region 22a arranged in a checkered flag shape (checkered pattern) on the main surface of the base material 22. That is, on the main surface of the base material 20 with a film, the first film 24 and the exposed portion (second region 22b) of the base material 22 are alternately present.

FIG. 4 is a schematic plan view showing an example of the substrate with a film of the present invention. As shown in FIG. 4, the film-attached base material 30 has a base material 32 and a first film 34 arranged in a band-shaped first region 32a on the main surface of the base material 32. The second region 32b on the main surface of the base material 32 is exposed on the main surface of the base material 30 with a film.

The shape of the first film 34 is a band-shaped straight line, but is not limited to this, and may be a band-shaped curve (for example, a wavy line) or a band-shaped polygonal line (for example, herringbone). The shapes of the plurality of first films 34 may be the same or different from each other, but are preferably the same as shown in FIG.
The width of the first film 34 is preferably 10 to 100,000 μm (10 cm), more preferably 50 to 20,000 μm (2 cm), from the viewpoint that the effect of the present invention is more excellent. The widths of the plurality of first films 34 may be the same or different from each other, but are preferably the same as shown in FIG.
The first film 34 is arranged at equal intervals, but the arrangement is not limited to this, and the arrangement intervals of the first film 34 may be different. The arrangement spacing of the first film 34 is preferably 10 to 1500 μm, more preferably 50 to 800 μm, from the viewpoint that the effect of the present invention is more excellent.

FIG. 5 is a schematic plan view showing an example of the substrate with a film of the present invention. The base material 42 has a peripheral region 42b (second region 42b) and a central region 42a (first region 42a) surrounded by the peripheral region 42b on its main surface. As shown in FIG. 5, the film-attached base material 40 has a base material 42 and a first film 44 arranged in the central region 42a. The peripheral region 42b on the main surface of the base material 42 is exposed on the main surface of the base material 40 with a film.

The shape of the first film 44 is a quadrangle (more specifically, a rectangle), but is not limited to this, and is not limited to, for example, a circular shape, an elliptical shape, an oval shape, a crossed oval shape, or a polygonal shape (for example, a polygonal shape). (Triangle, pentagon, hexagon, cross, star, etc.), or the polygon may have rounded corners. Among these, a quadrangle is preferable because the effect of the present invention is more excellent.
The area of the first film 44 can be appropriately set according to the area of the main surface of the base material, but the area ratio between the area of the first film 44 and the area of the peripheral region 42b is set so as to have a relationship described later. It is preferable to do so.

FIG. 6 is a schematic plan view showing an example of the substrate with a film of the present invention. The base material 52 has a plurality of point-shaped dispersion regions 52b (second region 52b) and continuous regions 52a (first region 52a) other than the dispersion region 52b on its main surface. As shown in FIG. 6, the film-attached base material 50 has a base material 52 and a first film 54 arranged in the continuous region 52a. The dispersion region 52b on the main surface of the base material 52 is exposed on the main surface of the base material 50 with a film.
It can be said that the dispersed region 52b corresponds to the dispersed phase (island portion) in the sea-island structure, and the continuous region 52a corresponds to the continuous phase (sea portion) in the sea-island structure.

The shape of the dispersion region 52b is, but is not limited to, a cross (more specifically, the “X” shape of the alphabet), for example, a circular, oval, oval, or oval intersecting shape. It may be a polygon (for example, a triangle, a quadrangle, a pentagon, a star, etc.) or a rounded corner of the polygon. Among these, a quadrangle is preferable because the effect of the present invention is more excellent.
The shapes of the plurality of dispersion regions 52b may be the same or different from each other, but are preferably the same as shown in FIG.
The size of the dispersion region 52b is preferably 10 to 1500 μm, more preferably 50 to 800 μm, from the viewpoint that the effect of the present invention is more excellent. Here, the size of the dispersion region 52b means the diameter of the dispersion region 52b when the shape is circular, and means the equivalent circle diameter calculated from the area of the dispersion region 52b when the shape of the dispersion region 52b is not circular. ..
The sizes of the plurality of dispersion regions 52b may be the same or different from each other, but are preferably the same as shown in FIG.
The dispersion regions 52b are arranged at equal intervals, but the present invention is not limited to this, and the dispersion regions 52b may be randomly arranged. The distance between the adjacent dispersion regions 52b is preferably 10 to 100,000 μm (10 cm), more preferably 50 to 20,000 μm (2 cm), from the viewpoint that the effect of the present invention is more excellent.

In each of the main surfaces of the base material with a film in FIGS. 1 to 6, a part of the main surface of the base material is exposed from the portion where the first film is not arranged, but the main surface is not limited to this, and the base material is not limited to this. A second film (described later) having no poly (oxyfluoroalkylene) chain may be arranged on at least a part of the second region on the main surface of the above.

The area ratio between the first region and the second region (area of the first region / area of the second region) is preferably 0.3 to 50.0, more preferably 0.5 to 45.0, and 0.6. ~ 40.0 is particularly preferable. When the area ratio is 0.3 or more, the fingerprint stain removing property of the substrate with a film is excellent. When the area ratio is 50.0 or less, the slip resistance of the substrate with a film is excellent.

When the base material is composed of a material containing silicon atoms (preferably glass), the coverage of the first film on the main surface of the base material with a film is preferably 20 to 97%, more preferably 50 to 95%. It is preferable, and 60 to 93% is particularly preferable. When the coverage of the first film is 20% or more, the fingerprint stain removing property of the substrate with the film is more excellent. In particular, when the coverage of the first film is 60% or more, the fingerprint stain removing property of the film-coated substrate is excellent, and the friction resistance of the film-coated substrate is also excellent. When the coverage of the first film is 97% or less, the slip resistance of the substrate with a film is more excellent.
In calculating the coverage, the main surface of the base material with a film means the surface of the surface on which the first film is formed (for example, the surface 12X in FIG. 2).
Here, the coverage of the first film, the time-of-flight secondary ion mass spectrometry (TOF-SIMS), F ₂ of the main surface of the film-coated substrate ^- Retrieves the mapping image, which is image analysis It can be calculated by The value calculated in this way is used as the coverage of the first film.
The second region preferably has a continuous and constant area. The continuous area of the second region ^{is preferably 0.001 mm 2} or more and 1 cm ² or less, and ^{more preferably 0.01 mm 2} or more and 0.1 cm ² or less. If it is 0.001 mm ² or more, the slip resistance is good. If it is 1 cm ² or less, the fingerprint removal property is excellent.

(Physical characteristics)
The difference between the dynamic friction coefficient a of the first film and the dynamic friction coefficient b of the portion corresponding to the second region on the main surface of the substrate with the film (dynamic friction coefficient b-dynamic friction coefficient a) is 0.01 to 0.99. Preferably, 0.05 to 0.6 is more preferable, and 0.1 to 0.5 is particularly preferable. When the difference in dynamic friction coefficient is 0.01 or more, the fingerprint stain removing property of the substrate with a film is excellent. When the difference in dynamic friction coefficient is 0.99 or less, the slip resistance of the substrate with a film is excellent.
The coefficient of kinetic friction of the portion of the main surface of the substrate with a film corresponding to the second region means the coefficient of kinetic friction of the second film when the second film (described later) is formed in the second region. When the second film is not formed in the second region, it means the coefficient of dynamic friction of the base material.
The coefficient of kinetic friction a is preferably 0.01 to 0.4, and particularly preferably 0.01 to 0.3.
The dynamic friction coefficient b is preferably more than 0.4, and particularly preferably 0.5 to 0.8.
For the dynamic friction coefficient, the dynamic friction coefficient of the part corresponding to the first film or the second region for the artificial skin (Idemitsu Technofine Co., Ltd., PBZ13001) is used by the load-variable friction and wear test system (Shinto Kagaku Co., Ltd., HHS2000). , Contact area: 3 cm x 3 cm, load: 0.98 N.

The film thickness of the first film is preferably 1 to 100 nm, particularly preferably 1 to 50 nm. The thickness of the first film is determined by obtaining an interference pattern of reflected X-rays by the X-ray reflectivity method using an X-ray diffractometer for thin film analysis (ATX-G: product name, manufactured by RIGAKU). It can be calculated from the vibration cycle of.

[Second film]
On the main surface of the base material with a film (the surface of the surface on which the first film is arranged), the portion corresponding to the second region of the base material is composed of the base material itself (that is, the mode in which the base material is exposed). It may be composed of a film having no poly (oxyfluoroalkylene) chain (hereinafter, also referred to as “second film”).
As a specific example of the second film, a base film formed on the main surface of the base material by treating the base material with the compound described in paragraphs 0008 to 0905 of International Publication No. 2011/016458 or SiO _{2 or the like.} A film formed on the main surface of the base material using the above.
The second film may be formed on the entire second region or may be formed on a part of the second region.

[Manufacturing method of substrate with film]
The substrate with a film of the present invention can be produced by arranging the first film only in the first region of the main surface of the substrate.
More specifically, by using a fluorine-containing ether compound or a composition containing a fluorine-containing ether compound and a liquid medium (hereinafter, also referred to as “composition”), the production conditions of both dry coating and wet coating can be used. , The first film can be formed only in the first region of the main surface of the base material.

Specific examples of the liquid medium contained in the composition include water and an organic solvent. Specific examples of the organic solvent include a fluorine-based organic solvent and a non-fluorine-based organic solvent.
The organic solvent may be used alone or in combination of two or more.

Specific examples of the fluorinated organic solvent include fluorinated alkanes, fluorinated aromatic compounds, fluoroalkyl ethers, fluorinated alkylamines, and fluoroalcohols.
The fluorinated alkane is preferably a compound having 4 to 8 carbon atoms, for example, C ₆ F ₁₃ H (AC-2000: product name, manufactured by AGC Inc.), C ₆ F ₁₃ C ₂ H ₅ (AC-6000: product name). , AGC), C ₂ F ₅ CHFCHFCF ₃ (Bertrel: product name, manufactured by DuPont).
Specific examples of the fluorinated aromatic compound include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, 1,3-bis (trifluoromethyl) benzene, and 1,4-bis (trifluoromethyl) benzene.
The fluoroalkyl ether is preferably a compound having 4 to 12 carbon atoms, for example, CF ₃ CH ₂ OCF ₂ CF ₂ H (AE-3000: product name, manufactured by AGC Inc.), C ₄ F ₉ OCH ₃ (Novec-7100:). Product name, C ₄ F ₉ OC ₂ H ₅ (Novec-7200: Product name, manufactured by 3M), C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ (Novec-7300: Product name, 3M).
Specific examples of the fluorinated alkylamine include perfluorotripropylamine and perfluorotributylamine.
Specific examples of the fluoroalcohol include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, and hexafluoroisopropanol.

As the non-fluorine-based organic solvent, a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, and specifically, a hydrocarbon-based organic solvent and a ketone-based organic solvent are used. , Ether-based organic solvent, ester-based organic solvent, alcohol-based organic solvent can be mentioned.
Specific examples of the hydrocarbon-based organic solvent include hexane, heptane, and cyclohexane.
Specific examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
Specific examples of the ether-based organic solvent include diethyl ether, tetrahydrofuran, and tetraethylene glycol dimethyl ether.
Specific examples of the ester-based organic solvent include ethyl acetate and butyl acetate.
Specific examples of the alcohol-based organic solvent include isopropyl alcohol.

The content of the fluorine-containing ether compound in the composition is preferably 0.01 to 50.00% by mass, particularly preferably 1.0 to 30.00% by mass, based on the total mass of the composition.
The content of the liquid medium in the composition is preferably 50.00 to 99.99% by mass, particularly preferably 70.00 to 99.00% by mass, based on the total mass of the composition.

The base material with a film can be produced, for example, by the following method.
-The main surface of the base material is treated by a dry coating method using a fluorine-containing ether compound or a composition to obtain the above-mentioned base material with a film in which the first film is arranged only in the first region of the main surface of the base material. Method.
A method in which the composition is applied to the main surface of a base material by a wet coating method and dried to obtain the above-mentioned article in which the first film is arranged only in the first region of the main surface of the base material.

Specific examples of the dry coating method include a vacuum deposition method, a CVD method, and a sputtering method. Among these, the vacuum vapor deposition method is preferable from the viewpoint of suppressing the decomposition of the fluorine-containing ether compound and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a metal porous body such as iron or steel with a fluorine-containing ether compound or a composition may be used.
When the dry coating method is used, as a method of arranging the first film only in the first region of the main surface of the base material, after arranging a mask having a shape corresponding to the first film on the main surface of the base material, dry coating is performed. A method of treating the main surface of the base material by a method can be mentioned.
Specific examples of the mask include a metal mesh having an opening, a punching sheet having a hole, an adhesive tape, and printing with a resin or paint.
The wire diameter of the metal mesh is preferably 80 to 500 μm, and particularly preferably 100 to 500 μm, in that the coverage of the first film can be easily set in the above range.
The opening of the metal mesh is preferably 150 to 2000 μm, particularly preferably 200 to 1500 μm, in that the coverage of the first film can be easily set in the above range.
The spacing between the holes of the punching sheet is preferably 70 to 1000 μm, and particularly preferably 70 to 700 μm, in that the coverage of the first film can be easily set in the above range.
The opening of the punching sheet is preferably 100 to 1000 μm, particularly preferably 200 to 700 μm, in that the coverage of the first film can be easily set in the above range.
It is preferable to use the adhesive tape as a mask and to apply resin or paint, particularly preferably to use printing as a mask, because the shape can be freely adjusted in figures such as circles and quadrangles, characters, and patterns. The resin or paint may be curable or plastic, and a photocurable resin or paint is preferable because the shape can be easily adjusted. Further, it is preferable that these resins and paints are easily dissolved in water or a solvent because they are easy to peel off.

Specific examples of the wet coating method include spin coating method, wipe coating method, spray coating method, squeegee coating method, dip coating method, die coating method, inkjet method, flow coating method, roll coating method, casting method, Langmuir Brodget. The method and the gravure coat method can be mentioned.
When the wet coating method is used, as a method of arranging the first film only on the first region of the main surface of the base material, a mask is placed on the main surface of the base material as in the dry coating method, and then the wet coating method is used. The composition may be applied to the main surface of the substrate.
It is preferable to use the adhesive tape as a mask and to apply resin or paint, particularly preferably to use printing as a mask, because the shape can be freely adjusted in figures such as circles and quadrangles, characters, and patterns.
Among the wet coating methods, if the inkjet method is used, the first film can be arranged only in the first region of the main surface of the base material without using a mask.

The first film formed by the above procedure contains a compound obtained through a hydrolysis reaction and a condensation reaction of a fluorine-containing ether compound.

[Other application forms]
The substrate with a film of the present invention can also be applied to articles requiring design. Specifically, for building materials, decorative building materials, interior goods, transportation equipment, signboards / bulletin boards, drinkers / tableware, water tanks, ornamental equipment, laboratory equipment, furniture, glass or resin used for art / sports / games, etc. Applicable. The shape of the base material may be plate-like or film-like.
Since regions having different surface free energies are formed on the surface of these base materials, when water droplets adhere, the shape of the region to which the water droplets adheres differs. Due to this difference, the scattering, reflection, and transmission of light change, so that designs such as characters and patterns can be displayed. Specifically, for example, when cold water is poured into tableware or drinking glasses to cool them, letters, symbols, and patterns emerge. Also, for example, when glass used for window glass, mirrors, aquariums, bulletins, sports games, etc. condenses, letters, symbols, patterns, pictures, and designs emerge. Examples of the method of causing dew condensation include a method of causing a temperature difference between the base material and air by cooling / raising the temperature, a method of increasing the humidity, and the like. Specific examples include a method of cooling with ice, a method of humidifying, and a method of blowing breath.
Further, since regions having different surface free energies are formed on the surface of these base materials, when fingerprints, oils, or stains are attached, light scattering, reflection, or transmission changes depending on the amount of the adhesion. As a result, designs such as characters and patterns can be displayed. Specifically, for example, fingerprints are attached by touching the back surface of a smartphone or glass used for sports games, and characters, symbols, patterns, pictures, and designs are attached depending on the difference in the amount of fingerprints attached in areas with different fingerprint adhesion. It can be used for the emergence of.
Water is poured into tableware, water tanks, and glass used for sports, games, and art, and patterns are made to stand out depending on the presence or absence of water in the water-repellent part that repels water and the hydrophilic part where water collects, and glass used for laboratory equipment. One example is to pour a liquid into a container and separate the part where the liquid collects.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples. The blending amount of each component indicates the mass standard. Of Examples 4 to 18, Examples 5 to 7, 10, 12, 13, 15, 17 and 18 are Examples, and Examples 4, 8, 9, 11, 14 and 16 are Comparative Examples.

〔Evaluation methods〕

(Coverage)
The main surface of the base material with a film (the first film is arranged) by a device (TOF.SIMS5: product name, manufactured by ION-TOF) based on the time-of-flight secondary ion mass spectrometry (TOF-SIMS). It was analyzed surface), using an analysis software _{(surface Lab 6.7), F 2} - a mapping image by binning (binning) in 64 pixels were ROI (Region of Interest) analysis. With the minimum value (Min) of the threshold value (Min) being 40% and the maximum value (Max) being 100%, the presence or absence of coating was determined for each binned region, and it was determined that there was coating with respect to the total number of binned regions. The percentage of the number of regions was calculated. This ratio (%) was defined as the coverage of the first film.
The measurement conditions by TOF-SIMS are as follows.
Measurement mode: High Current Bunched Mode
Primary ion species: Bi ₅ ⁺⁺
Acceleration voltage of primary ion: 25kV
Current value of primary ion: 0.05pA @ 10kHz
Cycle time: 100 μs
Mapping mode: 2D Large Area Mode
Raster: sawtooth, 1 shots / pixel
Number of Scans: 1
Frames per Patch: 8
Field of Analysis: 5 x 5 mm ²
Pixel Density: 256 pixels / mm
Maximum Patch Side Length: 0.25mm
Detector Extractor without surface potential adjustment (Use Surface Potential): 2000V
Detector Energy without surface potential adjustment (Use Surface Potential): 2000V
Use of electron gun: Yes

(Water contact angle)
The contact angle (water contact angle) of about 2 μL of distilled water placed on the main surface (the surface on which the first film is placed) of the base material with a film is measured by a contact angle measuring device (DM-500: product name, Kyowa Interface Science). It was measured using (manufactured by the company). Measurements were made at five different points on the main surface, and the average value was calculated. The 2θ method was used to calculate the contact angle.
⊚ (good): The contact angle is 100 degrees or more.
◯ (possible): The contact angle is 80 degrees or more and less than 100 degrees.
X (defective): The contact angle is less than 80 degrees.

(Fingerprint stain removal property)
Fingerprints adhering to the main surface of the base material with a film (the surface on which the first film is placed) are wiped off with a cellulose non-woven fabric (Bencot M-3: product name, manufactured by Asahi Kasei Co., Ltd.), and the ease of removal is visually judged. did. The judgment criteria are shown below.
◎ (Good): Fingerprints can be completely wiped off.
○ (Yes): Fingerprint wiping marks remain.
× (Defective): Fingerprint wiping marks spread and cannot be wiped.

(Abrasion resistance)
The evaluation test for fingerprint stain removal was carried out on the evaluation sample after the abrasion resistance test, and the fingerprint stain removal was evaluated according to the same evaluation criteria. The better the fingerprint removal property after the friction resistance test, the smaller the deterioration of the performance due to friction, and the better the friction resistance.
<Abrasion resistance test>
The main surface of the base material with a film (the surface on which the first film is placed) is made of cellulose using a reciprocating traverse tester (manufactured by KNT) in accordance with JIS L0849: 2013 (ISO 105-X12: 2001). A non-woven fabric (Bencot M-3: product name, manufactured by Asahi Kasei Co., Ltd.) was reciprocated 10,000 times at a load of 1 kg, a friction length of 4 cm, and a speed of 30 rpm.

(Slip resistance)
A fully automatic contact angle meter (DMo-701; product name, manufactured by Kyowa Surface Chemical Co., Ltd.) in which the main surface was held horizontally was prepared. A base material with a film is placed on the surface (horizontal plane) of a polyethylene sheet (hard polyethylene sheet (high density polyethylene): product name, manufactured by Hagitech Co., Ltd.) so that the arrangement surface (main surface) of the first film is in contact. Then, gradually tilt it using a fully automatic contact angle meter, and the angle (sliding) between the surface on which the first film of the film-coated substrate is formed and the horizontal plane when the film-coated substrate begins to slide down. Angle) was measured. The judgment criteria are shown below. The contact area between the base material with a film and the polyethylene sheet was 6 cm × 6 cm, and the measurement was performed under the condition that a load of 0.98 N was applied to the base material with a film.
◎ (Good): The sliding angle is 5 degrees or more.
○ (Yes): The sliding angle is 2 degrees or more and less than 5 degrees.
X (defective): The sliding angle is less than 2 degrees.

[Example 1: Synthesis example]
Compound 3A was obtained with reference to the method for producing compound (ii-2) described in International Publication No. 2014/126064.
Compound _{3A: CF 3 CF 2 -OCF 2} CF 2 - (OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2) mA -OCF 2 CF 2 CF 2 -C (O) NH-CH 2 CH 2 CH 2 -Si (OCH ₃ ) ₃
Mean of mA: 13, number average molecular weight of compound 3A: 4,920.

[Example 2: Synthesis example]
Compound 3B was obtained according to the method described in Example 2 of WO 2017/038832.
Compound _{3B: CF 3 CF 2 CF 2} -OCHFCF 2 -OCH 2 CF 2 - {(OCF 2) mB1 (OCF 2 CF 2) mB2} -OCF 2 -CH 2 -N [CH 2 CH 2 CH 2 -Si ( OCH ₃ ) ₃ ] ₂
Mean value of mB1: 21, mean value of mB2: 20, number average molecular weight of compound 3B: 4,470.

[Example 3: Synthesis example]
Compound 3C was obtained according to the method described in Example 11 of WO 2017/038830.
Compound 3C: CF _3- (OCF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CF ₂ ) _mC (OCF ₂ CF ₂ ) -OCF ₂ CF ₂ CF _2- C (O) NH-CH _2- C [CH ₂ CH _2] CH _2- Si (OCH ₃ ) ₃ ] ₃
Mean value of mC: 13, number average molecular weight of compound 3C: 5,400.

[Example 4]
Compound 3A and hydrofluoroether (Novec HFE7200: product name, manufactured by 3M Ltd.) were mixed to obtain a composition having a concentration of compound 3A of 20% by mass.
Using the obtained composition, the surface of the base material is treated by the following vacuum vapor deposition method to form a part of the main surface of the chemically strengthened glass (Dragontrail glass; product name, manufactured by AGC) which is the base material. An evaluation sample (base material with a film) on which the first film was formed was obtained. The surface treatment of the base material was carried out after a mask having holes (a metal mesh manufactured by MISUMI, an opening of 80 μm, a wire diameter of 50 μm) was attached to the main surface of the base material.
Specifically, a silicon dioxide film (thickness 7 nm) is formed on the main surface of the base material under a pressure of 3.0 × 10 ^{-3 Pa for vacuum vapor deposition, followed by one piece of chemically strengthened glass (55 mm).} 2 mg of the composition (ie, 0.4 mg of compound 3A) was deposited per x 100 mm). Next, the substrate with a vapor-deposited film was allowed to stand for 24 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 65%, and then washed with AK-225 (product name, manufactured by AGC Inc.) to cover the main surface of the substrate. An evaluation sample (base material with a film) in which the first film was partially arranged was obtained.
When the main surface (the surface on which the first film was arranged) of the obtained evaluation sample was _{confirmed from the image analysis result of the F 2} ^- stage scan mapping image, the composition vacuum-deposited on the shaded portion of the mask was found. It wraps around, and the first film is arranged on the entire main surface. It is considered that the reason for this is that the small wire diameter of the metal mesh reduces the adhesion between the base material and the mask.
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

[Examples 5 to 18]
An evaluation sample (base material with a film) was obtained in the same manner as in Example 4 except that the types of the fluorine-containing ether compound and the mask were changed as shown in Table 1.
Specifically, in Examples 5, 6, 9, 10 and 12, a metal mesh (manufactured by MISUMI) having a mesh size and a wire diameter shown in Table 1 was used as a mask. In Examples 7, 13, 15 and 17, a copper foil punching sheet (manufactured by Fukuda Metal Leaf Powder Industry Co., Ltd.) having openings and hole spacings shown in Table 1 was used as a mask. In Examples 8, 11, 14 and 16, no mask was used.
In Example 18, the following evaluation samples were prepared. A photocurable paint (RIP-1C manufactured by Jujo Chemical Co., Ltd.) was applied to a glass substrate, and a metal halide lamp was irradiated with a punching metal having an opening of 100 μm and a hole spacing of 110 μm as a mask. Then, it was washed with warm water to remove the uncured paint. As a result, a glass substrate on which the cured film was printed in a circular shape was prepared. Vacuum deposition was performed in the same manner as in Example 4 except that compound 3B was used instead of compound 3A. The printed matter was removed using an ultrasonic cleaner while immersed in an ethanol solution. The remaining paint was physically peeled off. A sample was obtained in which Compound 3B was attached to a portion other than the printed portion (the portion of the hole of the punching metal) (Compound 3B was adhered to the same shape as the punching metal).
The fluorine-containing ether compound used in Examples 15 and 16 is Optool UD509 (product name, manufactured by Daikin Industries, Ltd.), which is a compound having a poly (oxyfluoroalkylene) chain and a reactive silyl group.
Incidentally, an example 5～7,9,10,12,13,15,17 and 18, the main surface of the evaluation sample obtained (the surface on which the first layer is disposed) _{F 2} ^- Stage Scan mapping image image As a result of confirmation from the analysis results, it was confirmed that the first film of each shape shown in Table 1 was formed. The shape of the first film is shown in Table 1.
However, in Example 9, the vacuum-deposited composition wraps around the shaded portion of the mask, and the first film is arranged on the entire main surface. It is considered that the reason for this is that the small wire diameter of the metal mesh reduces the adhesion between the base material and the mask.
The above-mentioned evaluation test was carried out using the obtained evaluation sample, and the results are shown in Table 1.

As shown in Table 1, if the first film is arranged only in a part of the main surface of the base material (Examples 5 to 7, 10, 12, 13, 15, 17 and 18), fingerprint stain removal property and slip resistance It was confirmed that a substrate with a film having excellent properties could be obtained.
On the other hand, when the first film was arranged in the entire region of the main surface of the base material (Examples 4, 8, 9, 11, 14 and 16), it was confirmed that the slip resistance was inferior.

The base material with a film of the present invention can be used for various applications in which water and oil repellency is required. For example, display input devices such as touch panels; transparent glass or transparent plastic members, antifouling members for kitchens; water- and moisture-repellent and antifouling members such as electronic devices, heat exchangers, and batteries; antifouling members for toiletries. A member that requires liquid repellency while conducting; a member for water repellency / waterproofing / sliding of a heat exchanger; a member for surface low friction such as a vibrating sieve or the inside of a cylinder. More specific examples of use include a display front protective plate, an antireflection plate, a polarizing plate, an antiglare plate, or those having an antireflection film treatment on their surfaces, a mobile phone (for example, a smartphone), and a mobile information terminal. , Game machines, devices such as remote controls, touch panel sheets, touch panel displays, and other devices that have a display input device that operates on the screen with human fingers or the palm of the hand (for example, glass or film used for the display unit, etc., and Glass or film used for exterior parts other than the display part), decorative building materials around water such as toilets, baths, washrooms, kitchens, waterproof members for wiring boards, water-repellent / waterproof / sliding members for heat exchangers, sun Water-repellent material for batteries, waterproof / water-repellent material for printed wiring boards, waterproof / water-repellent material for electronic device housings and electronic parts, waterproof / water-repellent material for power transmission lines, waterproof / water-repellent material for various filters Materials, waterproof materials for radio wave absorbers and sound absorbing materials, antifouling materials for baths, kitchen equipment, toiletries, surface low friction materials such as vibrating sieves and cylinders, mechanical parts, vacuum equipment parts, bearing parts, automobiles, etc. Examples include parts for transportation equipment, surface protection members such as tools, and the like.

In addition, it can be used for various purposes for which designability is required.
For example, building materials such as windows used for exteriors of houses and buildings, decorative building materials such as mirrors, signs, bulletin boards, screens, baths, parts for transportation equipment used for water tanks, cars and airplanes, art, sports. , Materials used for games, kitchen utensils such as tableware such as cups, bottles, plates and drinking bottles, experimental equipment such as beakers, measuring cylinders and humidity meters, mobile phones (for example, smartphones), mobile information terminals, games Used for exterior parts (excluding display parts) in equipment such as machines and remote controls; examples include transparent glass or transparent plastic members.
When the base material with the main film is used as the member, the article having the member may have a plurality of the base materials with the main film. Further, the article having the above-mentioned member may have a base material having a covering ratio of more than 80 to 100% (preferably 100%) of the fluorine-containing ether compound in addition to the base material with the main film. In that case, the preferable range and examples of the fluorine-containing ether compound are the same as those of the fluorine-containing ether compound used for the base material with the main film. However, when it is used for applications that require designability, there is no particularly preferable value as an appropriate value for the coverage.
The specification, claims, abstract and drawings of Japanese Patent Application No. 2018-050077 filed on March 16, 2018 and Japanese Patent Application No. 2018-181620 filed on September 27, 2018. The entire contents of the above are cited here and incorporated as disclosure of the specification of the present invention.

10, 20, 30, 40, 50 Base material with film 12, 22, 32, 42, 52 Base material 12a, 22a, 32a 1st region 12b, 22b, 32b 2nd region 12X, 12Y surface 14, 24, 34, 44, 54 First film 42a Central region (first region)
42b Peripheral area (second area)
52a continuous area (first area)
52b Distributed region (second region)
t Thickness direction

Claims (10)

A base material with a film, comprising a base material and a film having a poly (oxyfluoroalkylene) chain arranged only in a partial region on the main surface of the base material. The membrane-coated substrate according to claim 1, wherein the membrane is a membrane obtained by using a fluorine-containing ether compound having a poly (oxyfluoroalkylene) chain and a reactive silyl group. Area ratio of the first region, which is the region where the film having the poly (oxyfluoroalkylene) chain is arranged, to the second region, which is the region where the film having the poly (oxyfluoroalkylene) chain is not arranged. The film-coated substrate according to claim 1 or 2, wherein the area of the first region / the area of the second region) is 0.3 to 50.0. The base material with a film according to any one of claims 1 to 3, wherein the base material is a touch panel base material or a display base material. The film-coated substrate according to any one of claims 1 to 4, wherein the substrate is made of glass and the coverage of the film having a poly (oxyfluoroalkylene) chain on the main surface is 20 to 97%. .. The film-coated substrate according to any one of claims 1 to 5, wherein the film is arranged in a plurality of punctate regions on the main surface of the substrate. The film-coated substrate according to claim 6, wherein the plurality of dot-shaped regions are arranged in a checkered flag shape. The film-coated substrate according to any one of claims 1 to 5, wherein the film is arranged in a band-shaped region on the main surface of the substrate. The base material has a peripheral region and a central region surrounded by the peripheral region on its main surface.
The film-attached substrate according to any one of claims 1 to 5, wherein the film is arranged in the central region. The base material has a plurality of point-like dispersion regions and continuous regions other than the dispersion regions on the main surface thereof.
The film-attached substrate according to any one of claims 1 to 5, wherein the film is arranged in the continuous region.

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